Composition of matter

ABSTRACT

A COMPOSITION CONSISTING ESSENTIALLY OF CERTAIN RELATIVELY WATER INSOLUBLE BRIGHTENERS ESSENTIALLY COMPLETELY DISSOLVED IN AN ACIDIC SOLVENT WHICH FORMS A DETERGENT WHEN IT IS NEUTRALIZED; PROCESSES FOR PREPARING SAID COMPOSITION; AND THE CORRESPONDING NEUTRALIZED COMPOSITION.

United States Patent 3,579,458 COMPOSITION OF MATTER Joseph E. Callen and Robert D. Haxby, Springfield Township, Hamilton County, and William T. Fagin, Colerain Township, Hamilton County, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Continuation-impart of application Ser. No. 517,941, Jan. 3, 1966. This application May 8, 1968, Ser. No. 727,654

Int. 'Cl. Clld 3/42 US. Cl. 252-152 8 Claims ABSTRACT OF THE DISCLOSURE A composition consisting essentially of certain relatively water insoluble brighteners essentially completely dissolved in an acidic solvent which forms a detergent when it is neutralized; processes for preparing said composition; and the corresponding neutralized composition.

This application is a continuation-in-part of our copending application, Ser. No. 517,941, filed Jan. 3, 1966, for Composition of Matter, which is now abandoned.

This invention relates to new compositions of matter containing specific optical brighteners which are relatively water insoluble and to processes for preparing detergent compositions utilizing said new compositions of matter.

Certain optical brighteners which are relatively insoluble in water are particularly eflective for use in detergent compositions which are used to wash, e.g., such synthetic textiles as Nylon and Dacron. It has been discovered that detergent compositions containing these relatively water insoluble optical brighteners must contain the optical brighteners in a highly dispersed form if maximum deposition of the optical brighteners on the article to be cleaned is to be achieved within the short time in which the textile is in the wash solution. Apparently the optical brighteners must first become solubilized in the aqueous wash solution and then deposit out on the textiles. If the optical brighteners are incorporated in the detergent composition in the form of large particles, the rate of solution or dispersion is too slow and insufficient time is available in the washing cycle for the brighteners to become solubilized or dispersed in the wash solution and to deposit out on the textiles. In order to disperse these relatively water insoluble brighteners in solid detergent compositions such as spray dried granules it has been suggested that the brighteners be dissolved in such materials as alcohol prior to adding the brighteners to the detergent slurry which is subsequently spray dried to form detergent granules. This process involves adding an extraneous material, i.e., the alcohol, to the detergent slurry, which in turn requires that the alcohol be subsequently removed during the spray drying. This method is wasteful.

It is an object of this invention to provide compositions of matter containing relatively water insoluble optical brighteners in solubilized form, suitable for incorporation in detergent compositions.

It is a further object of this invention to provide an efficient process for incorporating relatively water insoluble optical brighteners into detergent compositions, especially anionic detergent compositions.

3,579,458 Patented May 18, 1971 ice It is a still further object of this invention to provide a composition comprising relatively water insoluble optical brighteners in highly dispersed form in a paste of organic anionic detergent compound.

It is a still further object to provide a process for preparing said paste.

This object and other objects can be achieved by providing a composition consisting essentially of:

(1) An acidic solvent selected from the group consisting of (a) alkyl benzene sulfonic acid wherein the alkyl group contains from about 9 to about 15 carbon atoms, (b) monoesters of fatty alcohols containing from about 8 to about 20 carbon atoms with sulfuric acid, (c) monoesters of condensation products of from about 1 to about 10 moles of ethylene oxide with one mole of fatty alcohol containing from about 8 to about 20 carbon atoms with sulfuric acid and (d) mixtures thereof, said acidic solvents also containing from about 0.5% to about 50% sulfuric acid;

(2) A bn'ghtener selected from the group consisting of (a) brighteners having the formula A C-B-R wherein A is selected from the group consisting of and B B is selected from the group consisting of ---CH=CH;

wherein A has the meaning given hereinbefore and each R is selected from the group consisting of hydrogen atoms, alkyl groups containg from one to about twelve carbon atoms, alkoxy groups containing from one to.

about six carbon atoms, alkyl amino groups containing from one to about six carbon atoms, dialkyl amino groups containing from two to about twelve carbon atoms, chlorine atoms, fluorine atoms, bromine atoms, phenyl groups, styryl groups, cyano groups, carboxyl groups, esters of carboxyl groups and alcohols containing from one to about six carbon atoms, amino groups, substituted alkyl groups containing from one to about six carbon atoms substituted with an amino group or an arnido group containing from two to about six carbon atoms, aralkyl and alkaryl groups containing from seven to about 15 carbon atoms, and groups having the formula R O(R O) wherein R is an alkyl group containing from one to about 3 carbon atoms, R is a difunctional alkyl group containing from one to about three carbon atoms, and x is a number from one to about five; and D can be either an oxygen atom or a sulfur atom; brighteners having the formula wherein R is selected from the group consisting of R and groups having the formula G r? i R N N-Y 'wherein R has the definition given hereinbefore and R is selected from the group consisting of alkyl groups containing from one to about six carbon atoms, phenyl groups, and alkaryl and aralkyl groups containing from seven to about ten carbon atoms; brighteners having the v formula wherein each R has the definition given hereinbefore and Y is selected from the group consisting of chlorine and bromine atoms; brighteners having the formula wherein each R is selected from the group consisting of hydrogen atoms and alkyl groups containing from one to about six carbon atoms and R is a group having the formula -N(R wherein each R group is selected from the group consisting of alkyl groups containing from one to about twelve carbon atoms, alkaryl groups containing from seven to about ten carbon atoms, aralkyl groups containing from seven to about ten carbon atoms, phenyl, alkylene groups containing from two to about six carbon atoms, diphenyl, diphenyl ether, pyridinyl, hydrogen, chlorophenyl, dichlorophenyl, morpholino, and thiophene groups; brighteners having the formula wherein D, R and R are as defined above; and mixtures thereof, said acidic solvent being in liquid form, said brightener being dissolved in said acidic solvent and said brightener being present in an amount greater than about 0.001% by Weight of said acidic solvent up to the limit of the brighteners solubility in the acidic solvent and said brightener being essentially completely dissolved in said acidic solvent.

The above compositions can be prepared in two ways. For example, in a preferred and highly unobvious manner, they can be prepared by a process in which a relatively water insoluble brightener, as disclosed hereinbe fore and more specifically disclosed hereafter, is added to a neutral solvent selected from the group consisting of (a) alkyl benzene wherein the alkyl group contains from about 9 to about 15 carbon atoms, (b) fatty alcohols wherein said alcohols contain from about 8 to about 20 carbon atoms, (c) condensation products of from about 1 to about 10 moles of ethylene oxide with one mole of fatty alcohol containing from about 8 to about 20 carbon atoms, and (d) mixtures thereof, said neutral solvent being in liquid form, and thereafter introducing into the molecules of said neutral solvent, acid radicals by reacting said neutral solvents with a material selected from the group consisting of sulfonating agents and sulfating agents at a temperature ranging from about 20 F. to about P. so that neutral solvent (:1) is sulfonated and neutral solvents (b) and (c) are sulfated. The resulting reaction mixture is the acidic solvent, which has been described hereinbefore.

The upper limit of sulfuric acid in the acidic solvent is set by practical considerations. There is no real need to use an excess of sulfonating or sulfating agent which is sufficiently large to give a concentration of sulfuric acid greater than about 50%. The lower limit of sulfuric acid in the acidic solvent is set by the fact that a slight amount of even the strongest sulfonating or sulfating agent is always unreacted and that an excess is needed to drive the reaction.

The reaction mixture will dissolve more of the brightener than the neutral solvent and accordingly the amount of optical brighteners which are added to the neutral solvent is not limited by the solubility of the optical brighteners in the neutral solvent, but rather by the solubility of the optical brighteners in the reaction mixture (acidic solvent). The amount of brighteners present in the reaction mixture is from about 0.001% by weight of said reaction mixture up to the limit of the brighteners solubility in said reaction mixture after the reaction is finished. Said brighteners are essentially dissolved in said reaction mixture. It is surprising that the optical brighteners of this invention can withstand the rigors of sulfonation and/or sulfation without being modified or harmed.

The brighteners can, of course, be added directly to the above reaction mixture after the completion of the reaction rather than being added to the material which will be sulfonated and/ or sulfated. This method is straight forward.

The brighteners of this invention are the brighteners disclosed in the following patents: Belgian 568,115; British 828,545; British 903,810; British 916,555; British 941,048; British 942,518; British 967,360; British 967,- 483; British 990,397; British 1,007,017; British 1,010,749; British 1,026,368; British 1,033,385; British 1,037,378; British 1,045,818; Canadian 765,822; French 1,457,557; United States 2,977,319; United States 3,158,610; United States 3,169,960; United States 3,322,680.

These patents, and especially the brighteners disclosed therein, are incorporated herein by reference.

Specific examples of the brighteners of this invention are disclosed hereinafter in the examples. It is preferred that alkyl substituents of the brighteners of this invention contain from one to about six carbon atoms and preferably the alkyl substituents are methyl or ethyl groups. The preferred halogen is chlorine. Dialkyl substituents in, e.g., amino groups can be joined either by carbon to carbon bonds or through an oxygen atom to form ring structures. These brighteners are representative of relatively water insoluble brighteners which have particular effectiveness, e.g., when incorporated in detergent compositions which are used to wash such synthetic textiles as Nylon and Dacron. These brighteners are particularly effective in brightening the aforesaid synthetic textiles as well as other textiles when incorporated into detergent compositions as hereinbefore described.

The alkyl radicals in the aforesaid alkyl benzenes and alkyl benzene sulfonic acids can be either straight or branched chain radicals or mixtures thereof. The source of these radicals is not critical and they can be derived from natural sources such as triglycerides, e.g., coconut oil, or built up from smaller molecules such as in tetrapropylene. They can also be derived from petroleum fractions, either by separation or by splitting larger alkyl radicals. The alkyl group can be saturated as desired. Straight chain alkyl groups are desirable and preferable because they are biodegradable.

The fatty alcohols mentioned hereinbefore can be derived from natural sources such as by reduction (hydrogenation) of fatty acids of e.g., coconut oil and tallow, or reduction of the corresponding glycerides such as e.g., coconut oil and tallow. The alcohols can also be prepared by synthetic means from petroleum hydrocarbons. The source of the alcohols is not critical to the practice of this invention.

The sulfonating agents hereinbefore mentioned are selected from the group consisting of sulfur trioxide; complexes of sulfur trioxide with other compounds, e.g., sodium chlorosulfonate (complex with NaCl) and complexes of S with diethyl ether, pyridine, and/or dioxane; oleum having a concentration of from about 0% to 60% S0 sulfamic acid; and/or chlorosulfonic acid. The sulfating agents hereinbefore mentioned include all of the sulfonating agents hereinbefore described and sulfuric acid having a concentration of from about 90% to 100% H 50 The composition hereinbefore described comprising the acidic solvent and the brighteners hereinbefore specified has utility in that when the acidic solvent is neutralized pastes of organic anionic detergent compounds are formed in which the brighteners are contained in an extremely finely divided form. The type of neutralization agent is not critical from the standpoint of this invention. Suitable bases include hydroxides, oxides, carbonates and bicarbonates wherein the cations are ammonium, substituted ammonium (e.g., monoethanol-, diethanoland triethanolammonium), sodium, potassium, lithium, magnesium, ammonium, calcium and barium cations. Preferably, the base used to neutralize the acidic solvent is one which will give a water soluble organic anionic detergent compound. Bases containing the sodium cation are especially preferred. Preferably, the amount of base used will be at least suflicient to stoichiometrically react with the acidic solvent to give an essentially neutral paste.

The pastes as prepared by the above processes have particular utility in that they contain the brighteners in an extremely finely divided form even though the brighteners are not soluble in the neutralized paste, as such, to any appreciable extent.

The above pastes can be dehydrated to form solid detergent compositions in the form of granules, flakes, bars, etc. However, more commonly, and preferably, the above pastes are added to crutchers or to other mixing devices with other conventional components of detergent compositions to form detergent slurries which are then dehydrated to form detergent compositions in the form of eg, flakes, granules, bars. The above pastes can also be diluted with water to form aqueous liquid detergent compositions containing very fine dispersions of the optical brighteners. These fine dispersions are kept suspended more easily than coarser dispersions. Sufficient paste is used in forming the detergent compositions of this invention to provide from about 1% to about of the organic anionic detergent compounds in the finished detergent compositions.

Typical additives to detergent compositions which can be used with the pastes described hereinbefore, are detergency builders of inorganic and organic types. Not only do these detergency builders aid detergency, but in the case of the inorganic builders, they promote the formation of suitable solid forms of the detergent compositions when the organic anionic detergent compounds themselves do not readily form solid detergent compositions. The builder can constitute up to about by weight of the detergent composition. However, when the inorganic builders are used at high levels the solid detergent compositions tend to be brittle. Preferably, inorganic builders comprise from about 25% to about 75% of the detergent composition. When lower levels of inorganic builders are used, the amount of inert inorganic salts and/or other diluents is normally higher.

The builder canbe added separately in particulate form to solid particulate compositions formed from the hereinbefore mentioned pastes if desired.

Examples of water soluble inorganic alkaline builder salts which can be used, alone or in admixture with themselves (and organic alkaline sequestrant builder salts) are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, orthophosphates and hexametaphosphates. Examples of organic alkaline detergency builder salts are l) alkali metal amino polycarboxylates [e.g., sodium and potassium ethylenediaminetetraacetates, N (2 hydroxyethyl)-ethylenediaminetriacetates, nitrilo triacetates, and N-(2-hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytates see US. Pat. 2,739,942); (3) water soluble salts of ethanel-hydroxy-l,l-diphosphonate (e.g., the trisodium and tripotassium salts); (4) water soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium diphosphonate and the other salts described in US. Pat. 3,213,- 030); (5) water soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H, Roy, Ser. No. 266,055, filed Mar. 18, 1963); (6) water soluble salts of polycarboxylate polymers and copolymers as described in Diehls US. Pat. 3,308,067 (e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citronic acid and copolymers with themselves and other compatible monomers such as ethylene); and (7) mixtures thereof.

It is common to include in the detergent compositions of this invention from about 4% to about 16% of sodium and potassium silicates wherein the SiO :X O (wherein the X stands for sodium or potassium) ratio is from about 1.0 to about 3.4. These silicates are added as detergency builders and corrosion inhibitors. Diluents such as sodium sulfate and sodium chloride are also common ingredients. These diluents can be present in amounts up to about 90% of the detergent compositions of this invention.

Other minor ingredients can also be added to the detergent compositions of this invention. Soil suspending agents such as water soluble salts of carboxymethylcellulose and carboxyhydroxymethylcellulose are common components of detergent compositions of this type. Other optical brighteners can also be added. Dyes or pigments can be added if desired. Perfumes can also be added. Benzotriazole is a desirable optional ingredient which prevents corrosion of, e.g., German silver. The total amount of these minor ingredients is preferably less than about 10% by weight of the detergent compositions of this invention. These components can be added to the detergent compositions either separately or can be formed along with the organic anionic detergent compounds into solid detergent compositions.

The detergent compositions of this invention can also contain from to about of suds builders. and/or suds depressors. The suds builders are normally fatty acid amides wherein the fatty acid contains from about 8 to about 20 carbon atoms. These amides can be either normal amides, alkanol amides or alkyl amides wherein said alkanol groups contain from 1 to about 4 carbon atoms and from 1 to 2 hydroxy groups and said alkyl groups contain from 1 to about 4 carbon atoms. Mixtures of the above suds builders can also be used.

The suds depressors can be high molecular weight polyalkylene (propylene, ethylene and mixtures thereof) oxide compounds or high molecular Weight fatty acids containing from about 14 to about 31 carbon atoms or mixtures of the above. Specific and highly desirable suds depressors are those disclosed in US. Pats. 2,954,347 and 2,954,348.

All percentages, parts and ratios herein are by Weight unless otherwise specified.

The practice of this invention is demonstrated by the following example.

EXAMPLE Symmetrical 1,2(S-methylbenzoxazolyl)ethylene was added to a straight chain alkyl benzene which had an average chain length of 12 carbon atoms. There were .02 part of 1,,2-bis(S-methylbenzoxazolyl)ethylene for each 12.52 parts of the alkyl benzene.

A suflicient amount of the above mixture to contain 1,000 grams of the alkyl benzene was mixed with 1,030 grams of 30% oleum. The oleum was added to the alkyl benzene at a temperature of 120 F. The time of addition was five minutes. The mixture of oleum and alkyl benzene was held for an additional five minutes at 120 F. The mixture at this time contained alkyl benzene sulfonic acid and about 36% sulfuric acid (99.6%). The concentration of the brightener at this point was about .08%. Then 2,500 grams of Water and 1,450 grams of 50% sodium hydroxide solution was added to the mixture of oleum and alkyl benzene. The resulting paste containing sodium alkyl benzene sulfonate was held at 150 F. for five minutes to complete the neutralization of the alkyl benzene sulfonic acid.

The above paste was then added to a crutcher with sodium tripolyphosphate; sodium silicate having an SiO :Na O ratio of about 2; coconut middle-cut monoethanolamide, wherein coconut middle-cut refers to an acyl distribution wherein there are 2%-C 66%C 23%C and 9%-C acyl groups; water; sodium sulfate; and miscellaneous ingredients such as sodium carboxymethylcellulose and sodium toluene sulfonate. This crutcher mix was then spray dried and about 20 parts of moisture were removed in spray drying. The resulting spray dried granules contained:

about 17 percent sodium alkyl benzene sulfonate,

about 48 percent of sodium tripolyphosphate,

about 6 percent sodium silicate,

about 2 percent amide,

about 10 percent water,

about 2 percent miscellaneous ingredients,

about .02 percent of the 1,2(5-methylbenzoxazolyl)- ethylene,

and the balance sodium sulfate,

The resulting detergent granules contained the 1,2(5- methylbenzoxazolyl)ethylene in a highly dispersed form and the detergent composition was therefore extremely eifective in depositing said l,2(5-methylbenzoxazolyl)- ethylene on textiles such as Nylon and Dacron.

Other specific examples of this invention include the above compositions and processes of Example I when .02 part of the following brighteners are substituted for the .02 part of the 1,2-bis(S-methylbenzoxazolyl)ethylene and when 0.01 part of the following brighteners are substituted for .01 part of the 1,2-bis(S-methylbenzoxazolyl) ethylene. In all of these examples the brightener is also incorporated in the finished detergent granules in a highly dispersed form:

1,4-dibenzoxazolylthiophene;

4,4'-bis(5"-methylbenzoxazol-2-yl)stilbene;

4- 5 "-ethylbenzoxazol-2"-yl) -4- 5 -rnethoxy-benzoxazol- 2-yl)stilbene;

4 (5" ethylaminobenzoxazol 2" yl)-4-5"-(5"-dimethylaminobenzoxazol-Z"-yl)stilbene;

4 (5" acetamidobenzoxazol 2-yl)-4-(5"-chlorobenzoXazol-2"-yl stilbene;

4 (5" phenylbenzoxazol-Z"-yl)-4-(5"-cyanobenzoxazol-2"-yl) stilbene;

4 (5" styrylbenzoXaz0l-2"-yl) 4-(5-carboxybenzoxazol-2"-yl stilbene;

4 [5" carbethoxybenzoxazol-Z"-yl1-4-(5"-aminobenzoxazol 2"-yl) stilbene;

2-yl] stilbene; 4,4 bis (5 benzylbenzthiazol-Z '-yl stilbene 4,4'-bis( 5 '-ethylbenzoxazol-2"-yl stilbene; 4,4'-bis-6-methoxybenzylthiazol-2"-yl stilbene; 4,4'-bis 5 "-aminobenzylthiazol-Z"-yl stilbene; 1,2-bis( 6-phenylbenzoxazol-2'-yl) ethylene; 1,2-bis (5 -dimethy1aminobenzoxazol-2-yl) ethylene; 1,2-bis 6'-actamidobenzoxazol-2-yl ethylene; 2,5-bis benzoxazol-2'-yl thiophene; 2,5 -bis 5 '-chlorobenzoxazo1-2'-yl thiophene; 2,5-bis(naphtho[1,2-d]-oxazol-2'-yl)thiophene; 2,5-bis (benzoxazolyl-2-yl) -furan; 2,5-bis carboXybenzoxazoLZ-yl furan; 2-styryl-6-ethoxybenzoxazole; 2-styryl-5- (3 ',6-dioxa0ctyl benzoxazole; 2-styryl-5-phenylbenzylthiazole; 2,2- (p-phenylenedivinylene bis-benzoxazole; 2,2'- p-phenyenedi-vinylene bis 5 '-diethylaminobenzoxazole) 7 -dimethylamino-3 -phenylcoumarin; 6-ethyl-3-phenyl-coumarin; 4-dimethylamino- 1,8-N-phenylnaphthalimide 4-diethylamino-1,8-N-ethylnaphthalimide; 2-pheuyl-5- (5 -dodeclybenzoxazol-2'-yl) -thiophe ne;

4-cyanol ,8-naphthalimide 4-phenyl-1,8-N-butylnaphthalimide;

3,5-bis-ethylamino-2,fi-pyrazinedicarboxylamide;

3,5 -bis-methylaminopyrazine-2-methylcarboxylamide-6- phenylcarboxylamide;

3 ,5 -bis-butylamino-pyrazine-2-diethylcarboxylamide-6- ethylcarb oxylamide 3-phenylamino-S-ethylaminopyrazine-2,6-bis-methylcarboxylamide;

3,5 -bis-ethylaminopyrazine-2,6-bis-ethylcarboxylamide;

3,5 -bis-propylaminopyrazine-Z- 4'-methoxyphenyl carboxylamide-6- 2'-methylphenyl) carboxylamide;

3 ,5 -diaminopyrazine-Z-methylcarboxyl amide-6-ethyl- 'carboxylamide;

1,2-bis '-cyclohexylbenzoxazol-2'-yl ethylene;

1,2-bis( S-methylbenzoxazol-Z -ethylene;

7-amino-3- (p-triazinylaminophenyl) coumarin;

7-an1ino-3- (p-triazinylmethylaminophenyl coumarin;

4-propyl-3-(p-[4,6-dimethoxytriazin-2-yl1aminophenyl) coumarin;

7 -dimethylamino-4-ethyl-3 p-triazinylmethylaminophenyl coumarin;

7-amino-4-methyl-3- (p- [4-amino-6 ethoxytriazin-T-yl] propylaminophenyl) coumarin;

7-diethylamino-4-methyl-3- (p- [4,6-diaminotriazin-2- yl] amino phenylcoumarin;

7-butylamino-4-ethyl-3 -(p- [4-phenyl-6-( dihydroxyethyl) amino-triazin-Zyl] aminophenyl coumarin;

7-dimethylamino-5-methoxy-3- (p- 4',6 -dimethoxytriazin-2-yl] aminophenyl) coumarin;

7-methoxy-5-cyano-3- (p- [4',6-bis (diethylamino triazin 2-yl] methylaminophenyl)coumarin;

7-diethylamino-5-methyl-4-cyano-3- (p- [4',6'-dimethyltriazin-Z' yl] propylaminophenyl coum arin;

7 -acetamido-5-cyano-3- (p- [4,6-diethoxytriazin-2'-yl] aminophenyl) coumarin;

4-acetamido-5-cyano-7 2'-hydroxyethyl) -3 -methylcoumarin;

4-acetamido-3- (p- [4',6'-dihydroxyethylthiazin-2'-yl] methylamino) propylcoumarin;

3,5 -bis[diethylamino]pyrazine-2-methylcarboxylamide- -6-phenylcarb0xylamide;

2,5 -diphenyl-3-morpholinofuran;

2,5-diphenyl-3 -vinylfuran;

2,3,5 -triphenylfuran;

2,5-diphenyl-3 -N,N-diethylaminofuran 2, 5 -diphenyl-3-N,N-diethanolaminofuran;

2,5-diphenyl-3 -ethoxyfuran;

2,5-diphenyl-3-deca (oxyethylene furan;

2,5-di-p-chlorophenyl-3-morpholinofuran;

2,5-di-p-aminophenyl-3-morpholin0furan;

2,5-di-o,m-dichlorophenyl-3 -morpholinofuran;

2,5-diphenyl-3 -morpho1inopyrrole;

2,5 -diphenyl-3 -vinylpyrrole;

2,3,5 -tn'phenylpyrro1e 2, 5 -diphenyl-3-N,N-diethylamino pyrrole;

2, 5 -diphenyl-3 -N,N-diethanolaminopyrrole;

2,5-diphenyl-3 -ethoxypyrrole;

2,5-diphenyl-3-dicarb ethoxypyrrole;

2,5 -di-p-chlorophenyl-3 -morpholinopyrrole;

2,5-di-p-arninophenyl-3 -morpholinopyrrole;

2,5-di-o,m-dichlorophenyl-3-morpholinopyrrole;

2,5-diphenyl-3 -morpholinothiophene;

2,5-diphenyl-3 -vinylthiophene;

2,3 ,5 -triphenylthiophene;

2, 5 -diphenyl-3-N,N-diethylaminothio phene;

2,5 -dipheny13 -N,N-diethanolaminothiophene 2,5-diphenyl-3 -ethoxythiophene;

2,5-diphenyl-3 -deca (oxyethylene) thiophene;

2,5-di-p-chlorophenyl-3 -morpholinothiophene;

2,5-di-p-aminophenyl-3 -morph0linothiophene;

2,5-di-o,m-dichlorophenyl-3-morpholinothiophene; and

2,S-dinaphthyls llfonate-B-morpholinothiophene.

When in the above examples equal molar amounts of either coconut alcohol, tallow alcohol, condensation products of coconut alcohol and/or tallow alcohol with, e.g., 4 moles of ethylene oxide, or mixtures thereof, in e.g., 1:1 ratios by weight, are substituted either wholly or in part, e.g., in a 1:1 ratio by weight, for the alkyl benzene, substantially equivalent results are obtained in that the brighteners are present in the resulting detergent granules in a highly dispersed form.

When in the above examples equal molar amounts of the following sulfonating agents are substituted either wholly of in part for the 30% oleum, substantially equivalent results are obtained in that the alkyl benzene, and any alcohols which may be present, are sulfonated and/ or sulfated.

Sulfur trioxide, sodium chlorosulfonate, complexes of S0 'with diethyl ether, pyridine and/or dioxane, oleum having a concentration of 30% S0 sulfamic acid, chlorosulfonic acid, and mixtures thereof in, e.g., 1:1 ratios.

When in the above examples carbonates; pyrophosphates; ethylenediaminetetraacetates; N- Z-hydroxyethyl ethylenediaminetriacetates; nitrilo triacetates; N-(Z-hydroxyethyl)-nitrilodiacetates; phytates; ethane-l-hydroxyl-diphosphonates; methylenediphosphonates; ethylidene diphosphonates; isopropylidene diphosphonates; benzylmethylidene diphosphonates; chloromethylidene diphosphonates; salts of polymers of itaconic acid; aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene maleic acid and citronic acid; salts of copolymers of the above acids with themselves; salts of copolymers of the above acids with ethylene; salts of copolymers of the above acids with themselves and ethylene. (The foregoing named polymers and copolymers have molecular Weight of at least 350 and equivalent Weights of from 50 to based on the acid forms) and mixtures thereof in the form of their sodium, potassium, triethanolammonium, diethanolammonium, and monoethanolammonium salts and mixtures thereof are substituted, either wholly or in part, e.g., a 50% substitution, for the sodium tripolyphosphate builder substantially equivalent results are obtained in that the resulting detergent granules contain the optical brighteners in a highly dispersed form.

When in the above examples the alkyl benzene is completely replaced by coconut alcohol, tallow alcohol or condensation products of coconut alcohol, and/or tallow alcohol, with, e.g., 4 moles of ethylene oxide per mole of alcohol, then the 30% oleum can be completely replaced with H 50 With substantially equivalent results in that the corresponding sulfuric esters of the aforementioned alcohols are formed and the resulting granules contain the optical brighteners in a highly dispersed form.

When in the above example the following neutralization agents are substituted, either wholly or in part, for the sodium hydroxide, substantially equivalent results are obtained in that the corresponding detergent pastes are obtained with the brighteners in a highly dispersed form: hydroxides, oxides, carbonates and bicarbonates 'wherein the cations are ammonium, monoethanol ammonium, diethanola mmonium, triethanolammonium, sodium, potassium, lithium, magnesium, calcium and barium cations.

What is claimed is:

1. The process of preparing an acidic brightener-detergent precursor composition in which a brightener is highly dispersed in the brightener-detergent precursor composition consisting essentially of 1) adding to a neutral solvent selected from the group consisting of (a) alkyl benzene wherein the alkyl group contains from about 9 to about 15 carbon atoms, (b) fatty alcohols wherein said alcohols contain from about 8 to about 20 carbon atoms, (c) condensation products of from about 1 to about 10 moles of ethylene oxide with one mole of fatty alcohol containing from about 8 to about 20 carbon atoms, and ((1) mixtures thereof, said neutral solvent being in liquid form, a brightener selected from the group consisting of (1) brighteners having the formula N I %BR A wherein A is selected from the group consisting of B is selected from the group consisting of R is selected from the group consisting of i A \D wherein A has the meaning given hereinbefore and each R is selected from the group consisting of hydrogen atoms, alkyl groups containing from one to about twelve carbon atoms, alkoxy groups containing from one to about six carbon atoms, alkyl amino groups containing from one to about six carbon atoms, dialkyl amino groups containing from two to about twelve carbon atoms, chlorine atoms, fluorine atoms, bromine atoms, phenyl groups, styryl groups, cyano groups, carboxyl groups, esters of carboxyl groups and alcohols containing from one to about six carbon atoms, amino groups, substituted alkyl groups containing from one to about six carbon atoms substituted with an amino group or an amido group containing from two to about six carbon atoms, aralkyl and alkaryl groups containing from seven to about 15 carbon atoms, and groups having the formula R O'(R O) wherein R is an alkyl group containing from one to about 3 carbon atoms, R is a difunctional alkylene group containing from one to about three carbon atoms, and x is a number from one to about five; and D can be either an oxygen atom or a sulfur atom; (2) brighteners having the formula wherein R is selected from the group consisting of R and groups having the formula wherein each Y is selected from the group consisting of chlorine atoms, fluorine atoms, bromine atoms, amino groups having the formula N(R') and alkoxy groups containing from one to about six carbon atoms, and wherein R has the definition given hereinbefore; (3) brighteners having the formula wherein R has the definition given hereinbefore and R is selected from the group consisting of alkyl groups containing from one to about six carbon atoms, phenyl groups, and alkaryl and aralkyl groups containing from seven to about ten carbon atoms; (4) brighteners having the formula wherein each R has the definition given hereinbefore and Y is selected from the group consisting of chlorine and bromine atoms; (5) brighteners having the formula a 1 (R")2N\ o c /N\\ o r )2N \N N( )z 1 5 chlorophenyl, dichlorophenyl, morpholino, and thiophene groups; (6) brighteners having the formula wherein D, R and R are as defined above; and (7) mixtures thereof;

(2) introducing acid radicals into the molecules of the neutral solvent by reacting the neutral solvents with a material selected from the group consisting of sulfonating agents and sulfating agents so that the neutral solvent (a) is sulfonated and neutral solvents (b) and (c) are sulfated, in the reaction mixture, the amount of brightener present is from about 0.001% by Weight of the reaction mixture up to the limit of the brighteners solubility in said reaction mixture after the reaction is complete, and

(3) then neutralizing the reaction mixture with a neutralization agent selected from the group consisting of hydroxides, oxides, carbonates, and bicarbonates wherein the cations are ammonium, monoethanolammonium, diethanolammoniurn, triethanolammoniurn, sodium, potassium, lithium, magnesium, calcium, and barium cations.

2. The process of claim 1 wherein the neutral solvent is alkyl benzene and the sulfonating agent is 30% oleum.

3. The process of claim 1 wherein the sulfonating agent is selected from the group consisting of sodium chlorosulfonate, complexes of S0 with diethyl ether pyridine and dioxane, oleum having a concentration of from about 0% to about S0 sulfamic acid and chlorosulfonic acid.

4. The process of claim 1 wherein the sulfating agent is selected from the group consisting of sodium chlorosulfonate, complexes of SO with diethyl ether pyridene and dioxane, oleum having a concentration of from about 0% to about 60%, S0 sulfamic acid and chlorosulfonic acid, sulfamic acid having a concentration of from about to about H 50 5. The product formed by the process of claim 1.

6-. The product formed by the process of claim 2.

7. The product formed by the process of claim 3.

8. The product formed by the process of claim 4.

References Cited UNITED STATES PATENTS 2,873,206 2/1959 Geigy et a1. 117--33.5 2,944,028 7/1960 Stayner 252-161 2,972,509 2/1961 Olson 890X 3,238,249 3/1966 Mirviss et a1 260 405 3,309,392 3/ 1967 Roele 260458 3,400,124 9/1968 Okubo et a1. 117-33.5X

LEON D. ROSDOL, Primary Examiner M. HALPERN, Assistant Examiner US. Cl. X.R. 252137 

